基于磷和钾回收的黄水资源化处理技术研究
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摘要
基于未来可持续型城市排水系统的构建需求，本论文以黄水中磷和钾资源的回收为目标，研究了亚硝化/厌氧氨氧化和磷酸钾镁反应结晶的资源化处理工艺对黄水的处理效果，重点考察了磷酸钾镁的反应结晶特征，初步评估了黄水资源化处理系统的影响和价值。
考察了亚硝化/厌氧氨氧化SBR对黄水的脱氮效果。发现该工艺可以有效进行黄水脱氮，总氮和氨氮去除率高于90%，但是，黄水中较高的有机物浓度存在对SBR稳定运行的潜在威胁。成功开发了一种黄水的预处理方法用于消除有机物对脱氮工艺的潜在影响。在预留上部空间的密闭进水桶中接种挂膜后并定期复氧，可以有效地实现有机物的好氧降解和防止氨氮挥发损失。黄水预处理能明显缩短了SBR运行的周期时间，但周期时间的缩短不会显著影响脱氮效果。
考察了磷酸钾镁反应结晶法的影响因素和热力学特征。溶液pH值和Mg:K:P摩尔比是磷和钾回收的决定性因素。黄水中存在磷酸钾镁、磷酸铵镁和磷酸钠镁等鸟粪石系晶体的共结晶，结晶趋势强弱为：磷酸铵镁>磷酸钾镁>磷酸钠镁，这对于磷和钾回收具有重要影响。测算得到了MgKPO_4·6H_2O和MgNaPO_4·7H_2O的溶度积常数和反应标准摩尔焓变，分别为4.9×10~(-13)和2.2×10~(-12)、23.2和22.6kJ/mol。基于测定的热力学常数，利用PHREEQC软件建模模拟了黄水中的反应结晶，模拟结果得到了试验结果的良好验证。
考察了使用折流挡板式反应结晶器对黄水中磷和钾的回收效果。搅拌转速和水力停留时间是影响反应结晶器中结晶效率和晶体沉降性的关键性因素。适宜的搅拌转速为100~200r/min，水力停留时间为7.5~12.5h。反应结晶器可以对经过脱氮处理的真实黄水实现较好的磷和钾回收效果，磷和钾的回收率分别约为78%和90%。
基于上述研究结果和BioWIN软件，模拟评估了本论文提出的黄水资源化处理工艺，结果表明，黄水资源化能有效地降低城市生活污水处理系统的建设成本和运行成本，减少向污水环境中的氮磷排放负荷；同时，黄水中资源回收对国产磷肥产量的贡献有限，但是却能够较大的提升国产钾肥的产量，提高我国钾肥的自给率，缓解钾肥进口的压力。
Source separation and treatment of yellow water has been considered to bepart of sustainable sewerage system. Aiming to recover phosphorus andpotassium, this study investigated combined processes of nitrogen removal bynitritation/ANAMMOX (anaerobic ammonium oxidation) and nutrients recoveryby crystallization of magnesium potassium phosphate (MPP).
It was found that about90%removal of total nitrogen and ammonium wasachieved through nitritation/ANAMMOX using a sequence batch reactor (SBR).To avoid the negative effect of urine organic matter on the SBR, a pretreatmentprocess was developed to remove organic matter prior to the SBR. Thepretreatment of yellow water decreased cycle time of the reactor operatingwithout affecting the nitrogen removal efficiency.
Crystallization and thermodynamic characters of MPP were then studied.Solution pH and Mg:K:P molar ratio are the key factors influencing the recoveryof phosphorus and potassium. The co-crystallization of magnesium ammoniumphosphate, MPP and magnesium sodium phosphate (MSP) was confirmed viathe analysis on an X-ray diffractometer. The solubility products and standardmolar enthalpy change of reaction of MPP and MSP were calculated to be4.9×10~(-13)and2.2×10~(-12),23.23and22.65kJ/mol, respectively. Based on thethermodynamics, the crystallization in yellow water was modeled and thesimulation was well validated through batch experiments.
MPP crystallization was then investigated in a draft tube and baffle reactor(DTBR). Mixing speed and hydraulic retention time are important operatingfactors that influence crystallization efficiency and crystal settlement. Furtherapplications of the DTBR using real urine showed that about90%K and78%Pwere recycled to multi-nutrient products, respectively.
The effect of separation treatment of yellow water on existed wastewatertreatment system was studied via modeling using BioWIN. It was found that thetreatment of yellow water reduced the cost for constructing and operating anexistent wastewater treatment plant, and also decreased the emission of nitrogenand phosphorus to aquatic environment. Nutrients recovered from yellow water had a small contribution to phosphorus fertilizer production, but was valuable inimproving self-supplying of potassium fertilizer for China.
考察了亚硝化/厌氧氨氧化SBR对黄水的脱氮效果。发现该工艺可以有效进行黄水脱氮，总氮和氨氮去除率高于90%，但是，黄水中较高的有机物浓度存在对SBR稳定运行的潜在威胁。成功开发了一种黄水的预处理方法用于消除有机物对脱氮工艺的潜在影响。在预留上部空间的密闭进水桶中接种挂膜后并定期复氧，可以有效地实现有机物的好氧降解和防止氨氮挥发损失。黄水预处理能明显缩短了SBR运行的周期时间，但周期时间的缩短不会显著影响脱氮效果。
考察了磷酸钾镁反应结晶法的影响因素和热力学特征。溶液pH值和Mg:K:P摩尔比是磷和钾回收的决定性因素。黄水中存在磷酸钾镁、磷酸铵镁和磷酸钠镁等鸟粪石系晶体的共结晶，结晶趋势强弱为：磷酸铵镁>磷酸钾镁>磷酸钠镁，这对于磷和钾回收具有重要影响。测算得到了MgKPO_4·6H_2O和MgNaPO_4·7H_2O的溶度积常数和反应标准摩尔焓变，分别为4.9×10~(-13)和2.2×10~(-12)、23.2和22.6kJ/mol。基于测定的热力学常数，利用PHREEQC软件建模模拟了黄水中的反应结晶，模拟结果得到了试验结果的良好验证。
考察了使用折流挡板式反应结晶器对黄水中磷和钾的回收效果。搅拌转速和水力停留时间是影响反应结晶器中结晶效率和晶体沉降性的关键性因素。适宜的搅拌转速为100~200r/min，水力停留时间为7.5~12.5h。反应结晶器可以对经过脱氮处理的真实黄水实现较好的磷和钾回收效果，磷和钾的回收率分别约为78%和90%。
基于上述研究结果和BioWIN软件，模拟评估了本论文提出的黄水资源化处理工艺，结果表明，黄水资源化能有效地降低城市生活污水处理系统的建设成本和运行成本，减少向污水环境中的氮磷排放负荷；同时，黄水中资源回收对国产磷肥产量的贡献有限，但是却能够较大的提升国产钾肥的产量，提高我国钾肥的自给率，缓解钾肥进口的压力。
Source separation and treatment of yellow water has been considered to bepart of sustainable sewerage system. Aiming to recover phosphorus andpotassium, this study investigated combined processes of nitrogen removal bynitritation/ANAMMOX (anaerobic ammonium oxidation) and nutrients recoveryby crystallization of magnesium potassium phosphate (MPP).
It was found that about90%removal of total nitrogen and ammonium wasachieved through nitritation/ANAMMOX using a sequence batch reactor (SBR).To avoid the negative effect of urine organic matter on the SBR, a pretreatmentprocess was developed to remove organic matter prior to the SBR. Thepretreatment of yellow water decreased cycle time of the reactor operatingwithout affecting the nitrogen removal efficiency.
Crystallization and thermodynamic characters of MPP were then studied.Solution pH and Mg:K:P molar ratio are the key factors influencing the recoveryof phosphorus and potassium. The co-crystallization of magnesium ammoniumphosphate, MPP and magnesium sodium phosphate (MSP) was confirmed viathe analysis on an X-ray diffractometer. The solubility products and standardmolar enthalpy change of reaction of MPP and MSP were calculated to be4.9×10~(-13)and2.2×10~(-12),23.23and22.65kJ/mol, respectively. Based on thethermodynamics, the crystallization in yellow water was modeled and thesimulation was well validated through batch experiments.
MPP crystallization was then investigated in a draft tube and baffle reactor(DTBR). Mixing speed and hydraulic retention time are important operatingfactors that influence crystallization efficiency and crystal settlement. Furtherapplications of the DTBR using real urine showed that about90%K and78%Pwere recycled to multi-nutrient products, respectively.
The effect of separation treatment of yellow water on existed wastewatertreatment system was studied via modeling using BioWIN. It was found that thetreatment of yellow water reduced the cost for constructing and operating anexistent wastewater treatment plant, and also decreased the emission of nitrogenand phosphorus to aquatic environment. Nutrients recovered from yellow water had a small contribution to phosphorus fertilizer production, but was valuable inimproving self-supplying of potassium fertilizer for China.
引文
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